U.S. patent application number 12/743478 was filed with the patent office on 2010-10-07 for novel hydrophilic polyisocyanate compositions based on phosphate esters.
This patent application is currently assigned to Perstorp France. Invention is credited to Jean-Marie Bernard, Philippe Olier.
Application Number | 20100256286 12/743478 |
Document ID | / |
Family ID | 39387427 |
Filed Date | 2010-10-07 |
United States Patent
Application |
20100256286 |
Kind Code |
A1 |
Bernard; Jean-Marie ; et
al. |
October 7, 2010 |
NOVEL HYDROPHILIC POLYISOCYANATE COMPOSITIONS BASED ON PHOSPHATE
ESTERS
Abstract
The invention relates to a composition comprising at least one
(poly)isocyanate and at least one surfactant comprising an amino
acid and a mixture of compounds of formulae (I) and (II) wherein i
and j independently represent 0 or 1; and R.sub.1 et R.sub.2 are
identical or different and independently represent a
hydrocarbonated chain. Said mixture of compounds of formulae (I)
and (II) is characterised in that the molar ratio between compound
(II) and compound (I) is higher than 1. ##STR00001##
Inventors: |
Bernard; Jean-Marie;
(Saint-Laurent d' Agny, FR) ; Olier; Philippe;
(Lyon, FR) |
Correspondence
Address: |
COZEN O'CONNOR, P.C.
1900 MARKET STREET
PHILADELPHIA
PA
19103-3508
US
|
Assignee: |
Perstorp France
Saint-Preist
FR
|
Family ID: |
39387427 |
Appl. No.: |
12/743478 |
Filed: |
November 17, 2008 |
PCT Filed: |
November 17, 2008 |
PCT NO: |
PCT/FR08/52065 |
371 Date: |
June 4, 2010 |
Current U.S.
Class: |
524/507 ;
427/385.5; 524/500; 524/537; 524/539; 524/540; 524/589; 525/127;
525/418; 525/452 |
Current CPC
Class: |
C08G 18/706 20130101;
C08K 5/17 20130101; C08K 5/521 20130101; C08G 18/3885 20130101;
C08K 5/17 20130101; C08G 18/792 20130101; C08K 5/521 20130101; C08L
75/00 20130101; C08L 75/00 20130101 |
Class at
Publication: |
524/507 ;
525/452; 524/589; 524/500; 524/537; 524/540; 525/418; 525/127;
524/539; 427/385.5 |
International
Class: |
C08L 75/04 20060101
C08L075/04; C08L 69/00 20060101 C08L069/00; C08L 67/00 20060101
C08L067/00; B05D 3/02 20060101 B05D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 20, 2007 |
FR |
07 59173 |
Claims
1. A composition comprising: at least one (poly)isocyanate and at
least one surfactant comprising an amine and a mixture of compounds
based on the following formulae (I-1) and (II-1): ##STR00012## in
which: R.sub.1 and R.sub.2 are the same or different and represent,
independently, a hydrocarbon chain optionally substituted; said
mixture of compounds of formulae (I-1) and (II-1) being
characterised in that the molar ratio of compound (II-1) to
compound (I-1) is greater than 1.
2. The composition of claim 1, wherein the amine is an amine of the
following formula (III): ##STR00013## in which R.sub.3, R.sub.4 and
R.sub.5 represent, independently, H or a hydrocarbon chain
optionally substituted, the R.sub.3, R.sub.4 and R.sub.5 groups
optionally comprising at least one alkylene oxide group.
3. The composition of claim 1, wherein the amine is based on the
following formula (III-1): ##STR00014## in which: a is equal to 0,
1 or 2; R.sub.7 represents a hydrogen atom or a hydrocarbon chain;
and when a=0 the R.sub.7 groups may be the same or different and
may optionally form a cyclic structure comprising from 3 to 5
carbon atoms; R.sub.6 and R'.sub.6 are identical or different and
represent a hydrogen atom or a hydrocarbon chain; k represents an
integer greater than or equal to 1; k' represents an integer from 0
to 60; L.sub.1 and L'.sub.1 are the same or different and
represent, independently, a radical of formula -[-L'-O--].sub.t--,
t being an integer from 0 to 20, L' being a linear or branched
alkylene radical comprising from 3 to 10 carbon atoms, L' groups
being the same or different; L.sub.2 and L'.sub.2 are the same or
different and represent, independently, a linear or branched
divalent alkylene radical.
4. The composition of claim 1, wherein the composition comprises
from 3 to 30% by weight surfactant and from 70 to 97% by weight
(poly)isocyanate.
5. The composition of claim 1, wherein the amount of amine used
corresponds to the total neutralisation of the first acidity of the
mixture of compounds.
6. The composition of claim 1, wherein the (poly)isocyanate is a
(poly)isocyanate selected from the homo- or hetero-condensation
products of alkylene diisocyanate.
7. The composition of claim 1, wherein the (poly)isocyanate is a
(poly)isocyanate having an average functionality of isocyanate
functions at least equal to 2 and at most equal to 20.
8. The composition of claim 1, further including a solvent, the
amount of solvent in relation to the amount of the mixture formed
by the surfactant system and the (poly)isocyanate being lower than
50% by weight, the solvent being selected from the group formed of
esters, ethers, acetals, cyclic or linear carbonates, lactones,
glycol or propylene glycol ethers and N-alkyl amides.
9. The composition of claim 1, further comprising at least one
compound carrying at least one mobile hydrogen function selected
from the primary or secondary hydroxyl, phenol functions, primary
and/or secondary amine functions, carboxylic functions and SH
functions and, optionally, at least one organic solvent.
10. The composition of claim 9, comprising: from 10 to 60% by
weight (poly)isocyanate, relative to the total weight of the
composition without solvent, (% dry weight); from 0.25 to 12% by
weight surfactant, relative to the total weight of the composition
without solvent, (% dry weight); from 30 to 80% by weight compound
carrying at least one mobile hydrogen function, relative to the
total weight of the composition without solvent (% dry weight); and
from 0% to 30% by weight organic solvent, relative to the total
weight of the composition.
11. The composition of claim 9, wherein the compound carrying at
least one mobile hydrogen function is a polymer containing at least
two hydroxyl functions (alcohol or phenol) and/or thiol functions
and/or primary or secondary amine functions and/or containing
precursor functions of the epoxy or carbonate type which, upon
reaction with a suitable nucleophile, free the hydroxyl
functions.
12. The composition of claim 9, wherein the compound carrying at
least one mobile hydrogen function is a polyol selected from the
acrylic or polyester or polyurethane polymers.
13. The composition of claim 12, wherein the polyol has a
functionality of mobile hydrogen groups at least equal to 2.
14. The composition of claim 13, wherein the polyol has a
functionality of OH from 2 to 30, preferably from 2 to 10.
15. The composition of claim 9, wherein the average molecular
weight in numbers of the compound carrying at least one mobile
hydrogen function is between 100 and 100,000.
16. A process for preparing a composition according to claim 1,
comprising a step of mixing the compounds of formulae (I) and (II),
the amine and the (poly)isocyanate.
17. A process for producing a coated substrate, characterised in
that it comprises a step of applying a composition according to
claim 9 to a substrate and a step of cross-linking by thermal
treatment of said composition.
18. A coated substrate obtainable by the process according to claim
17.
19. (canceled)
Description
[0001] The present invention relates to new phosphate ester-based
hydrophilic polyisocyanate compositions, the process for the
preparation thereof and the use thereof to prepare coatings, in
particular paints or varnishes.
[0002] The fields of application in which coatings are used are
very varied and increasingly call for high-tech coating
compositions having excellent qualities with regard to both the
application of the coating and the characteristics of the finished
product.
[0003] There is incessant demand for coatings having improved
properties, in particular which those dry more quickly, are more
resistant to impact and shock, exhibit improved behaviour against
all types of chemical, organic, microbial or atmospheric attacks as
well as improved resistance to pressure washing, in particular for
substrates made of plastics materials.
[0004] International application WO 97/31960 in the name of the
Applicant company describes mixtures of monoesters and diesters of
ethoxylated phosphate.
[0005] Furthermore, international application WO 98/56843 describes
a polyisocyanate-based composition comprising triethylamine and a
mixture of mono- and di-(2-ethylhexyl)phosphate with 40% molar
weight monoester as well as a polyisocyanate-based composition
comprising triethylamine and a mixture of mono- and
di-(2-ethylhexyl)phosphate with 40% molar weight monoester.
[0006] The object of the present invention is to provide new
polyisocyanate compositions which make it possible to obtain
coatings which have satisfactory properties with regard to
homogeneity and shine.
[0007] The object of the present invention is to provide new
polyisocyanate compositions which, once applied to a substrate,
will make it possible to obtain a coating having a protective or
aesthetic function.
[0008] The present invention relates to compositions comprising:
[0009] at least one (poly)isocyanate and [0010] at least one
surfactant comprising an amine and a mixture of compounds based on
the following formulae (I) and (II):
##STR00002##
[0011] in which: [0012] i and j represent, independently, 0 or 1;
[0013] R.sub.1 and R.sub.2 are the same or different and represent,
independently, a hydrocarbon chain advantageously selected from
C.sub.6-C.sub.30 aryl groups and C.sub.1-C.sub.20 alkyl groups,
optionally substituted, advantageously C.sub.4-C.sub.10 alkyl
groups with at least one halogen, in particular a fluorine;
[0014] said mixture of compounds of formulae (I) and (II) being
characterised in that the molar ratio between compound (II), i.e.
the monoester-type compound, and compound (I), i.e. the
diester-type compound, is greater than 1, preferably from 1 to 10
and advantageously from 2 to 6.
[0015] The compositions according to the invention are referred to
hereinafter as phosphate ester-based hydrophilic polyisocyanate
compositions.
[0016] The choice of a specific monoester/diester molar ratio is
beneficial since it ensures that a film with a good appearance and
increased shine is achieved, said film being obtained by mixing
said hydrophilic polyisocyanate compositions with a
water-dispersible polyol or polyurethane (PUD), optionally in the
presence of a solvent.
[0017] The composition of (poly)isocyanates comprised in the
composition according to the present invention consists completely
of isocyanate and polyisocyanate, alone or in combination with one
or more other isocyanates and/or polyisocyanates. The term
"(poly)isocyanate" is to be understood in this case as encompassing
the terms "isocyanate" and "polyisocyanate".
[0018] The surfactant is advantageously selected in such a way that
it comprises no or few functions which are reactive with the
(poly)isocyanate. In other words, the surfactant is present in the
solvent-based composition in a substantially free form (in contrast
with a form bonded by means of a chemical bond to the
(poly)isocyanate).
[0019] The term "substantially free form" means that less than 50%,
advantageously less than 20%, preferably less than 10% by weight of
the surfactant is in a bonded form.
[0020] However, compositions in the form of a solution in which the
surfactant is completely bonded in a covalent manner to the
(poly)isocyanate are also included within the scope of the present
invention.
[0021] An advantageous composition according to the present
invention comprises a surfactant in which the amine is an amine of
the following formula (III):
##STR00003##
[0022] in which R.sub.3, R.sub.4 and R.sub.5 represent,
independently, H or a hydrocarbon chain, advantageously selected
from C.sub.6-C.sub.30 aryl groups and C.sub.1-C.sub.20 alkyl
groups, optionally substituted, in particular with at least a
halogen, preferably a fluorine, said alkyl groups being cyclic,
linear or branched,
[0023] the groups R.sub.3, R.sub.4 and R.sub.5 optionally
comprising at least one alkylene oxide group and preferably at
least one ethylene oxide group.
[0024] It is also possible that the R.sub.3, R.sub.4 and R.sub.5
groups form cyclic structures. R.sub.3 and R.sub.4 or R.sub.4 and
R.sub.5 or R.sub.3 and R.sub.5 may thus together form a cyclic
structure formed preferably of 3 to 5 carbon atoms and optionally
containing at least one heteroatom preferably selected from oxygen
or sulphur. N-ethyl morpholine, N-methyl morpholine and
1,2,2,6,6-pentamethylpiperidine are examples of cyclic structures
of this type.
[0025] Advantageously, in the aforementioned formula (III),
R.sub.3, R.sub.4 and R.sub.5 represent, independently, a
C.sub.6-C.sub.30 aryl group or a C.sub.1-C.sub.20 alkyl group.
N,N-dimethylcyclohexylamine, ethyldiisopropylamine,
dimethylbutylamine, dimethylbenzylamine, etc. are examples of
amines which may be suitable within the scope of the invention.
[0026] This embodiment relates to hydrophobic amines. Amines of
this type therefore do not contain an alkylene oxide group.
[0027] According to another advantageous embodiment, the
composition as defined above comprises an amine of formula (III) in
which at least one of the groups R.sub.3, R.sub.4 and R.sub.5
comprises at least one alkylene oxide group, preferably at least
one ethylene oxide group.
[0028] According to a further advantageous embodiment, the
composition as defined above comprises an amine of the following
formula (III-1):
##STR00004##
[0029] in which: [0030] a is equal to 0, 1 or 2; [0031] R.sub.7
represents a hydrogen atom or a hydrocarbon chain, advantageously
selected from the C.sub.1-C.sub.20 cyclic or non-cyclic alkyl
groups, preferably from the C.sub.1-C.sub.4 alkyl groups, or from
the aryl groups comprising from 6 to 30 carbon atoms; and when a=0,
the R.sub.7 groups may be the same or different and may optionally
form a cyclic structure comprising from 3 to 5 carbon atoms; [0032]
R.sub.6 and R'.sub.6 are the same or different and represent a
hydrogen atom or a hydrocarbon chain, advantageously selected from
the C.sub.1-C.sub.20 alkyl groups, preferably from the
C.sub.1-C.sub.4 alkyl groups, or from the aryl groups comprising
from 6 to 30 carbon atoms; [0033] k represents an integer greater
than or equal to 1, preferably greater than or equal to 2,
advantageously from 5 to 60, preferably from 5 to 40; [0034] k'
represents an integer advantageously from 0 to 60, preferably from
5 to 40; [0035] L.sub.1 and L'.sub.1 are the same or different and
represent, independently, a radical of formula -[-L'-O--].sub.t--,
t representing an integer from 0 to 20 and L representing a linear
or branched alkylene radical comprising from 3 to 10 carbon atoms,
L' preferably representing a --CH(CH.sub.3)--CH.sub.2-- or
--(CH.sub.2).sub.4-- radical, the t L' groups being the same or
different; [0036] L.sub.2 and L'.sub.2 are the same or different
and represent, independently, a linear or branched divalent
alkylene radical advantageously comprising from 1 to 20 carbon
atoms and preferably representing a --CH(CH.sub.3)--CH.sub.2-- or
--CH.sub.2--CH(CH.sub.3)-- radical.
[0037] According to a further embodiment, the composition of the
invention comprises a polyamine of the following formula (V):
(R.sub.7).sub.(2-a)-(D).sub.a-N-[L.sub.2-L.sub.1-(O--Z).sub.k--O-L'.sub.-
1-L'.sub.2-N(-D)].sub.g-L.sub.2-L.sub.1-(O--Z).sub.k--O-L'.sub.1-L'.sub.2--
N-(D).sub.a-(R.sub.7).sub.(2-a) (V)
[0038] in which: [0039] D represents H or
R.sub.6--(O--Z).sub.k--O-L.sub.1-L.sub.2- or R.sub.7, [0040] Z
represents an alkylene residue, optionally substituted, comprising
from 2 to 6 carbon atoms, Z preferably being an ethylene group,
[0041] g represents an integer from 0 to 5, preferably from 0 to 2,
[0042] a, k, R.sub.6, R.sub.4, L.sub.1, L.sub.2, L'.sub.1 and
L'.sub.2 are as defined above for formula (III-1).
[0043] The amine of the composition of the present invention is
preferably based on the following formula (A):
##STR00005##
[0044] in which: u.sub.1 represents an integer, preferably greater
than or equal to 2, advantageously from 5 to 60, preferably from 5
to 40, [0045] v.sub.1 represents an integer from 0 to 30,
preferably from 0 to 10, [0046] w represents an integer from 1 to
30, preferably from 1 to 10, [0047] R.sub.a represents an alkyl
group comprising from 1 to 20 carbon atoms, in particular a methyl
group or an alkyl group comprising from 12 to 14 carbon atoms, all
the R.sub.a groups being the same or different.
[0048] The amines preferred within the scope of the present
invention are as follows: [0049] an amine of formula (A) in which
v.sub.1 is not 0, R.sub.a represents a C.sub.12-C.sub.14 alkyl
radical with an ethylene oxide/propylene oxide ratio (u.sub.1/w)
equal to 9/2 (this amine is called Jeffamine.RTM. XTJ 247 and has a
molecular weight of approximately 700); or [0050] an amine of
formula (A) in which v.sub.1 is not 0, R.sub.a represents a methyl
group with an ethylene oxide/propylene oxide ratio (u.sub.1/w)
equal to 12/2 (this amine is called Jeffamine.RTM. XTJ 581 and has
a molecular weight of approximately 730).
[0051] The composition according to the invention particularly
advantageously contains a mixture of compounds based on the
following formulae (I-1) and (II-1):
##STR00006##
[0052] R.sub.1 and R.sub.2 being as defined above for formulae (I)
and (II).
[0053] A preferred composition according to the present invention
comprises from 3 to 30% by weight surfactant and from 70 to 90% by
weight (poly)isocyanate.
[0054] These values make it possible to obtain an emulsion suitable
for the various applications envisaged.
[0055] According to another advantageous embodiment, the
composition according to the present invention comprises from 5 to
25% by weight, preferably from 8 to 20% by weight, surfactant.
[0056] This preferred surfactant range further improves the
properties of the films obtained from the hydrophilic
polyisocyanate compositions of the invention.
[0057] The present invention also relates to a composition as
defined above, in which the amount of amine used corresponds to the
total neutralisation of the first acidity of the mixture of
compounds.
[0058] It is preferable to try to obtain a satisfactory rate of
neutralisation which corresponds to total neutralisation of the
first acidity of the mixture of compounds (I) and (II). This makes
it possible to further improve the properties of films obtained
from the hydrophilic polyisocyanate compositions of the
invention.
[0059] It is thus preferred to use a mole of amine for a mole of
acidic functions (corresponding to the first acidity carried by the
monoesters, diesters and phosphoric acid).
[0060] If the first acidity is not completely neutralised, this may
lead to problems with regard to the stability of the isocyanate.
Secondary reactions may take place between the NCO groups and the
OH groups corresponding to the first free acidity of the monoester
or the phosphoric acid which leads to a decrease in the NCO content
of the composition and a change in viscosity. In order to avoid
these problems, neutralisation at least greater than 50% of the
first acidity is generally preferred, preferably greater than 90%
of the first acidity and even more preferably greater than 110% of
the first acidity.
[0061] In order to determine the concentrations of monoester,
diester and H.sub.3PO.sub.4 from the evaluation of the acid values,
the process implemented for assaying phosphate esters using a
potassium or sodium hydroxide solution will be described
hereinafter.
[0062] Acid value means the number of milligrams of potassium
hydroxide necessary to neutralise 1 g of product. This value is
generally obligatorily given in mg or KOH, irrespective of the
titrant used. The method for measuring this value is described
hereinafter.
[0063] According to a preferred embodiment, the (poly)isocyanate of
the composition as defined above is a (poly)isocyanate selected
from the products of homo- or hetero-condensation of alkylene
diisocyanate, in particular comprising products of the biurate and
trimer type, even prepolymers with an isocyanate function, in
particular comprising urea, urethane, allophanate, ester, amide,
acylurea, isocyanurate, oxadiazinetrione, imino-dimer, imino-trimer
(imino-triazinedione), imino-oxadiazinedione (also known as an
asymmetric trimer) and diazetidinedione (also known as a dimer)
functions, and mixtures thereof.
[0064] The polyisocyanate compounds may also comprise true
carbonate functions (R--O--C(.dbd.O)--NH.sub.2) or epoxy functions
or (preferably cyclic) carbonate functions.
[0065] They may, for example, be polyisocyanates sold by Rhodia
under the name "Tolonate.RTM.".
[0066] The polyisocyanates which were used to prepare
water-dispersible polyisocyanate compositions have an NCO titre
generally comprised between 5 and 25%.
[0067] Specific monoisocyanates may be used to prepare
water-dispersible polyisocyanate compositions in order to modify
particular properties. An example of monoisocyanates of this type
are the isocyanate propyl trialkoxysilanes.
[0068] Other polyisocyanates with an NCO functionality greater than
2 may also be used to prepare hydrophilic polyisocyanate
compositions. Lysine diisocyanate isocyanatoethyl is another
example which reduces the viscosity of the final polyisocyanate
compositions.
[0069] It is also possible to use (poly)isocyanates as defined
above which are also rendered hydrophilic by grafting a suitable
hydrophilic additive.
[0070] Generally, preferred (poly)isocyanates are (poly)isocyanates
which are obtainable and generally obtained by homo- or
hetero-condensation of aliphatic isocyanate monomers, (cyclo or
aryl) aliphatic monomers, selected from the group consisting of the
following monomers: [0071] 1,6-hexamethylene diisocyanate, [0072]
1,12-dodecane diisocyanate, [0073] cyclobutane-1,3-diisocyanate,
[0074] cyclohexane-1,3 and/or 1,4-diisocyanate, [0075]
1-isocyanato-3,3,5-trimethyl-5-diisocyanatomethylcyclohexane
(isophorone diisocyanate, IPDI), [0076]
isocyanatomethyloctylenediisocyanates (TTI), [0077] 2,4 and/or
2,6-hexahydrotoluene diisocyanate (H.sub.6TDI), [0078]
hexahydro-1,3 and/or 1,4-phenylene diisocyanate, [0079] perhydro
2,4' and/or 4,4'-diphenylmethane diisocyanate (H.sub.12MDI), and in
general aromatic amino precursors or perhydrogenated carbamates,
[0080] bis-isocyanatomethylcyclohexanes (in particular 1,3 and 1,4)
(BIC), [0081] bis-isocyanatomethylnorbornanes (NBDI), [0082]
2-methylpentamethylene diisocyanate (MPDI), [0083]
tetramethylxylylene diisocyanates (TMXDI), [0084] lysine
diisocyanate as well as di-ou triisocyanate lysine esters (LDI ou
LTI), [0085] 2,4- and/or 2,6-toluene diisocyanate, [0086]
diphenylmethane-2,4' and/or 4,4'-diisocyanate (MDI), [0087] 1,3-
and/or 1,4-phenylene diisocyanate, [0088]
triphenylmethane-4,4',4''-triisocyanate, and [0089] oligomers of
MDI or of TDI.
[0090] The products of homocondensation are the products derived
from the condensation of one of the isocyanate monomers listed
above with itself. The products of heterocondensation are the
products derived from the condensation of two or more of the
monomers listed above, either together and/or optionally with one
or more mobile hydrogen compounds, such as an alcohol, a diol and
other similar compounds.
[0091] The polyisocyanates contained in the composition of the
present invention may also be polyisocyanate derivatives resulting
from aromatic isocyanates used alone or mixed with aliphatic
compounds.
[0092] However, the use of these aromatic derivatives is limited in
terms of the amount and is also not a preferred variant, since this
generally results in coatings which may undergo discolouration,
generally yellowing, as they age, particularly if the coatings are
exposed to a high degree of ultraviolet radiation, for example
solar ultraviolet radiation.
[0093] Examples of non-limiting aromatic isocyanates include:
[0094] 2,4- and/or 2,6-toluene diisocyanate, [0095]
diphenylmethane-2,4' and/or 4,4'-diisocyanate (MDI), [0096] 1,3-
and/or 1,4-phenylene diisocyanate, [0097]
triphenylmethane-4,4',4''-triisocyanate, and [0098] MDI or TDI
oligomers.
[0099] Mixtures of these (cyclo)aliphatic and/or aromatic
polyisocyanates may also be used.
[0100] The viscosity of the non-masked polyisocyanate compounds
used in the invention lies in a wide viscosity range determined by
the structure of the polyisocyanate compounds which may be used.
The viscosity is generally greater than 10 mPas at 25.degree. C.
with a non-volatile matter content of 100%, preferably greater than
100 mPas at 25.degree. C. with a non-volatile matter content of
100%.
[0101] The viscosity of Rhodia products is given by way of example,
such as Tolonate.RTM. HDT-LV2 which has a viscosity of
approximately 600 mPa.s.+-.150 mPa.s at 25.degree. C., or
Tolonate.RTM. HDT with a viscosity of 2,400 mPa.s.+-.400 mPa.s at
25.degree. C., or Tolonate.RTM. HDB with a viscosity of 9,000
mPa.s.+-.2,000 mPa.s at 25.degree. C., or Tolonate.RTM. HDT HR with
a viscosity of approximately 20,000 mPa.s at 25.degree. C. with a
non-volatile matter content of 100%, or 2,000 mPa.s at 25.degree.
C. with a non-volatile matter content of 90% in n-butyl
acetate.
[0102] Some polyisocyanate compounds are solid at a non-volatile
matter content of 100%. For example, this is the case for the IPDI
isocyanurate trimer or IPDI dimer. The viscosities of some of these
compounds in an organic solution are given by way of example;
Tolonate.RTM. IDT 70 S (IPDI isocyanurate trimer) thus has a
viscosity of approximately 1,700 mPa.s.+-.600 mPas at 25.degree. C.
for a formulation of 70% non-volatile matter in Solvesso.RTM. 100,
Tolonate.RTM. IDT 70 B (IPDI isocyanurate trimer) has a viscosity
of approximately 600 mPa.s.+-.300 mPas at 25.degree. C. for a
formulation of 70% non-volatile matter in n-butyl acetate.
[0103] Homocondensation and/or heterocondensation products
originating from an aliphatic, in particular non-cyclic,
diisocyanate monomer, preferably HDI, are preferred due to the
ability thereof to impart greater resistance to chipping to
coatings.
[0104] The present invention also relates to a composition as
defined above, in which the (poly)isocyanate is an (poly)isocyanate
having an average functionality of isocyanate functions at least
equal to 2 and at most equal to 20, preferably between 2.2 and 10,
advantageously between 3 and 6.
[0105] It has been observed that when the average functionality of
isocyanate functions of the (poly)isocyanate increases, i.e. the
resistance to chipping and the hardness of the coating are
improved, this phenomenon is particularly marked when it comes to
retouching.
[0106] Within the scope of the present invention, the average
functionality of isocyanate functions f(iNCO) is defined by the
following formula:
f ( iNCO ) = Mn .times. [ iNCO ] 42 .times. 100 ##EQU00001##
[0107] where: Mn represents the average molecular weight in numbers
obtained by gel permeation and
[0108] [iNCO] represents the concentration of isocyanate functions
in grams per 100 grams.
[0109] The (poly)isocyanates present in the composition according
to the invention may be present in masked form, that is to say that
the isocyanate functions are not free but are masked by a masking
agent or a mixture of masking agents, such as those defined below.
In particular, the use of masked (poly)isocyanate compositions is
preferred in order to prepare a mono-component coating formulation
type (formulation 1K).
[0110] "Masked (poly)isocyanate" is to be understood in the present
description as a (poly)isocyanate for which at least 50%,
preferably 80%, advantageously 90%, and more preferably all of the
isocyanate functions, are masked.
[0111] The masking agent or the mixture of masking agents which
temporarily or permanently protects the isocyanate functions are
compounds which have at least one function carrying a labile
hydrogen, generally a function carrying a labile hydrogen,
preferably a single function carrying a labile hydrogen and are
reactive in relation to the isocyanate function. This function
which carries a labile hydrogen may have a pKa value corresponding
either to the ionisation of an acid [including the hydrogen of -ol
functions ("-ol(s)" is to be understood in the present description
as phenols and alcohols)], or to the associated acid of a base
(generally nitrogenated).
[0112] More specifically, in order to optimise the results of the
present invention, said pKa (or one of them if a plurality thereof
can be determined) of the function carrying one or more labile
hydrogens is at least 4, advantageously 5, preferably 6 and at most
14, advantageously 13, preferably 12 and more preferably 10. An
exception thereto must be made for lactames, the pKa of which is
greater than these values and which represent potential masking
agents, although they are not preferred for the invention.
[0113] A masking agent is known as a temporary masking agent when
the isocyanate function is protected temporarily by the masking
agent and does not react under storage conditions for the
formulated system with hydroxyl functions of the mobile hydrogen
compound, in particular with polyol, but is subsequently freed
during the thermal cross-linking reaction in a furnace.
[0114] The freed isocyanate function therefore reacts with the
mobile hydrogen functions or the polyol reagent in order to produce
a urethane bond and to form a polyurethane network which forms a
portion of the coating. The temporary masking agent is either
eliminated as a volatile organic compound along with most of the
solvents in the formulation, or remains in the film, or reacts with
the aminoplastic resin when the formulation contains said
aminoplastic resin.
[0115] Non-limiting examples of temporary masking agents according
to the invention are hydroxylamine derivatives, such as
hydroxysuccinimide and oximes, such as methylethylketokime,
hydrozine derivatives such as pyrazoles, triazole derivatives,
imidazole derivatives, phenol derivatives or the like, amide
derivatives such as imides and lactames, hindered amines such as
N-isopropyl-N-benzylamine, as well as malonates or ketoesters and
hydroxamates. These compounds may also comprise substituents, in
particular alkyl chains.
[0116] In order to determine the pK.sub.a values defined above,
reference could be made to "The determination of ionization
constants, a laboratory manual", A. Albert of E. P. Serjeant;
Chapman and Hall Ltd, London".
[0117] For the list of masking agents, reference could be made to
Z. Wicks (Prog. Org. Chem., 1975, 3, 73 et Prog. Org. Chem., 1989,
9,7) and Petersen (Justus Liebigs, Annalen der Chemie 562, 205,
(1949).
[0118] Methylethylketoxime also known as MEKO,
3,5-dimethylpyrazole, also known as DMP, 2 or 4 alkylimidazoles,
dialkyl malonates, cyclic .beta.-keto-esters, amines, hindered
amines and caprolactame are preferred as temporary masking
agents.
[0119] The present invention is not limited only to temporary
masking agents but masking agents said to be permanent may also be
used. These are characterised by the fact that the isocyanate
functions are protected by the masking agent and do not react with
the hydroxyl functions of the mobile hydrogen compound, in
particular the polyol, under storage conditions of the formulated
system nor during the thermal cross-linking reaction in a
furnace.
[0120] The isocyanate functions are thus not restored at the time
of the cross-linking reaction effected by curing in a furnace and
remain masked, said masked functions thus being able to react in
the cross-linking conditions in a furnace with the methylol
(--N--CH.sub.2--OH) or alkoxyalkyl (--N--CH.sub.2--O-alkyl)
functions of the aminoplastic resins (melamine, benzoguanamine . .
. ), in the presence of an acidic, preferably sulphonic catalyst or
a latent precursor of said catalyst which may be a tertiary amine
salt or a sulphonic acid salt.
[0121] In some cases, the surfactant present in the coating
composition according to the invention may play the role of a
catalyst, in particular when the surfactant is of the anionic type
and comprises a phosphorus atom.
[0122] The masking agents used in order to permanently protect the
isocyanate function are generally compounds having hydroxyl or
sulphydryl functions, preferably monofunctional functions, such as
hydroxyl(cyclo)alkanes, for example methanol, butanols,
cyclohexanol, 2-ethylhexanol or compounds having carboxylic acid
functions, such as propionic acid, pivalic acid and benzanoic acid.
These compounds may optionally carry one or more substituents.
[0123] These masking agents which are said to be "permanent" may
also be isocyanate functions masked by compounds comprising at
least one cross-linkable function able to polymerise via UV
radiation. Examples of "permanent" masking agents are hydroxyalkyl
acrylates or hydroxyalkyl methacrylates.
[0124] In certain cases temporary bi- or poly-functional masking
agents comprising functions able to yield temporarily and/or
permanently masked isocyanate functions may also be used, generally
in limited amounts. However, this is not preferred since the masked
polyisocyanate compounds quickly exhibit high viscosities, and this
effect is all the more masked the further functionality of
isocyanate functions (NCO) increases.
[0125] The composition according to the invention may
advantageously also contain a solvent, the amount of solvent
relative to the amount of mixture formed by the surfactant system
and the (poly)isocyanate being less than 50% by weight, preferably
less than 40%, the solvent being selected from the group consisting
of esters, ethers, acetals, cyclic or linear carbonates, lactones,
glycol or propylene glycol ethers and N-alkyl amides.
[0126] The solvent is used in this embodiment in order to lower the
viscosity of the starting polyisocyanates.
[0127] This content of solvent is necessary, in particular in order
to use compounds such as IPDT which are solid at ambient
temperature and used in the form of formulations.
[0128] The content of solvent is minimised in order to avoid
compositions which are too rich in VOC (volatile organic
compounds).
[0129] The present invention also relates to a composition which is
cross-linkable by thermal treatment, as defined above, and further
comprises at least one compound carrying at least one mobile
hydrogen function selected from the primary or secondary hydroxyl
functions, phenol functions, primary and/or secondary carboxylic
functions, amine functions and SH functions and, optionally, at
least one organic solvent.
[0130] The composition as defined above preferably comprises:
[0131] from 10 to 60% by weight (poly)isocyanate, relative to the
total weight of the composition without solvent (% dry weight);
[0132] from 0.25 to 12% by weight surfactant, relative to the total
weight of the composition without solvent (% dry weight); [0133]
from 30 to 80% by weight compound, carrying at least one mobile
hydrogen function, relative to the total weight of the composition
without solvent (% dry weight); and [0134] from 0 to 30% by weight
organic solvent, relative to the total weight of the
composition.
[0135] The composition as defined above may advantageously also
comprise at least one aminoplastic resin ("aminoplast" resin) of
the melamine-aldehyde type, in particular melamine-formaldehyde,
and/or urea-aldehyde, in particular urea formaldehyde, or
benzoguanamine and/or the alkoxyalkyl derivatives thereof.
[0136] According to a preferred embodiment, the amount of
aminoplastic resin(s) in the composition as defined above is
between 15 and 25% by weight, relative to the total weight of the
composition without solvent (% dry weight).
[0137] The composition according to the present invention also
comprises an aminoplastic or aminoplast-type resin of the
melamine-formaldehyde and/or urea formaldehyde and/or
benzoguanamine-formaldehyde type. These polymers are known and
details relating to the synthesis thereof are given in the works
cited above, in particular in the book by Stoye and Freitag on page
102, chapter 6.2.
[0138] These aminoplastic resins react, in particular, at a
temperature between 100 and 180.degree. C. with the urethane
functions of the polyurethane network previously created or formed
during the cross-linking reaction in a furnace due to the freed
isocyanate functions reacting with the hydroxyl functions of the
polyol or with the true carbamate functions
(R--O--C(.dbd.O)--NH.sub.2) optionally carried by the polyols or
the polyisocyanates.
[0139] The cross-linking reaction of these melamines with the
urethane functions or true carbamate functions
(R--O--C(.dbd.O)--NH.sub.2) is a known reaction which is generally
catalysed by a strong acid, such as para-toluenesulphonic acid or
naphthalene-sulphonic acid, or even a latent form of said acid
catalysts, i.e. the tertiary amine salts of said strong acids.
Reference could be made to the books cited above in order to obtain
more detailed information regarding these aminoplastic resins and
the synthesis thereof.
[0140] The presence of one or more aminoplastic resins in the
coating composition according to the present invention is
particularly advantageous for the formation of the base coat and is
not generally necessary for the formation of the top coat, although
this is not excluded from the scope of the invention.
[0141] The present invention also relates to a composition as
defined above, in which the compound carrying at least one mobile
hydrogen function is a polymer containing at least two hydroxyl
(alcohol or phenol) functions and/or thiol functions and/or primary
or secondary amine functions and/or containing carboxylic acid
functions and/or containing precursor functions of the epoxy or
carbonate type which, by reacting with a suitable nucleophile, free
the hydroxyl functions.
[0142] The compounds are preferably selected from polyols which may
be used alone or in a mixture.
[0143] Examples of compounds of this type are dispersed polyols or
polyurethanes or polyamines or polythiols or polyacids or even
polycaprolactones-based polymers. These polymers may optionally
contain a plurality of mobile hydrogen functions. Mixtures of
polymers of this type may also be used. Generally, polyols selected
from polyesters, polyacrylates, polycaprolactones or polyethers or
mixtures thereof are preferred.
[0144] Polyesters or acrylic polyols or carbonate polyols or
polyurethane polyols will advantageously be contained in coatings
exposed to outside conditions.
[0145] Polyol compositions classed as latex may also be used. These
compounds are generally obtained by radical polymerisation of
compounds containing alkenyl functions, such as acrylates,
methacrylates, styrenyls, etc.
[0146] Even more preferably, the composition as defined above is
characterised in that the compound carrying at least one mobile
hydrogen function is a polyol selected from acrylic or polyester or
polyurethane polymers.
[0147] In order to enhance the flexibility of coatings and, in
particular, for the "primer" coat, it is preferred to use polyester
polyols or urethane polyesters. Generally, a mixture of two
polyester or urethane polyester resins is used, one resin being
characterised by a "hard" nature and the other by a "soft" or
"resilient" nature. The hard or soft nature of the polyesters is
conferred by the nature of the monomers during synthesis of said
polyesters.
[0148] A "hard" polyester is thus obtained by selecting aromatic
and/or cycloaliphatic and/or highly branched acid or alcohol
monomers. Examples of monomers of this type are phthalic anhydride
or cyclohexanediol or 2,2,4-trimethylpentanediol.
[0149] A "soft" polyester is obtained by selecting slightly
branched linear aliphatic monomers such as adipic acid or
1,4-butanediol or 1,6-hexanediol, or monomers which even comprise
heteroatoms in their structure, such as di- or
poly-ethyleneglycols. However, the latter are not desirable insofar
as these compounds exhibit a weakness with regard to their
stability to ultraviolet rays.
[0150] Polyester polyols are industrial products and their
synthesis is largely described and known to the person skilled in
the art. For more details, reference may be made to the following
works: "Materiaux polymeres, structure, proprietes et applications"
by Gottfried W. Ehrenstein and Fabienne Montagne published in 2000
by Hermes Science; "Handbook of Polyurethanes" by Michael Szycher,
published in 1999 by CRC press; "Resins for coatings, Chemistry,
Properties and Applications" by D. Stoye and W. Freitag, published
by Hanser in 1996, as well as the aforementioned Eurocoat 97
article. The commercial catalogues of companies which supply
polyols, in particular the book entitled "Specialty Resins,
creating the solution together" of AKZO NOBEL RESINS published in
February 2001 may also be consulted.
[0151] The polyol as defined above advantageously has a
functionality of mobile hydrogen groups at least equal to 2,
generally from 2 to 100, preferably from 2 to 30.
[0152] According to another advantageous embodiment, the polyol has
an OH functionality from 2 to 30, preferably from 2 to 10.
[0153] Generally, for the intended application, an OH functionality
which is too high will lead to compounds which are too "hard". It
is therefore preferred to use polyester polyols which have a
relatively low functionality which is lower than 15, preferably
lower than 10.
[0154] The definition of the average functionality of hydroxyl
functions per polymer chain, is, for example, given in the article
by Ben Van Leeuwen entitled "High solids hydroxy acrylics and
tightly controlled molecular weight" which appeared in the
conference series of Eurocoat 1997 (pp 505-515) on page 507.
[0155] This average functionality F(OH) is calculated using the
following equation:
F ( O H ) = O H number .times. Mn 56100 ##EQU00002##
[0156] in which: [0157] F(OH) represents the average functionality
of hydroxyl functions; [0158] OH number represents the titre of
hydroxyl functions expressed in mg of KOH (potassium hydroxide) per
gramme of polymer; and [0159] Mn represents the average molecular
weight in numbers of the polymer, determined by gel permeation
chromatography (GPC) by comparison with polystyrene calibration
standards.
[0160] The present invention also relates to a composition as
defined above, characterised in that the average molecular weight
in numbers of the compound carrying at least one mobile hydrogen
function is from 100 to 100,000.
[0161] According to a preferred embodiment, the composition as
defined above comprises a polyol which is a polyester polyol with
an average molecular weight in numbers from 500 to 10,000,
preferably from 600 to 4,000.
[0162] In certain cases, a polyol or a mixture of polyacrylic
polyols which afford the coating increased hardness may also be
used. These polyols may be "hard" or "soft" depending on whether
monomers having an aromatic and/or cycloaliphatic and/or heavily
branched nature for this "hard" property and monomers having a
primarily aliphatic nature for the "soft" property are used
respectively.
[0163] The synthesis of acrylic polyols is also known to the person
skilled in the art and reference may be made to the aforementioned
books for more details regarding their synthesis.
[0164] The average molecular weight in numbers for acrylic polyols
is generally between 134 and 50,000, preferably 500 and 25,000,
advantageously between 1,000 and 15,000.
[0165] The titre of hydroxyl functions is generally between 10 and
750 mg of KOH per gram of polymer, preferably between 15 and 500 mg
of KOH per gram of polymer.
[0166] For examples of acrylic polyols, reference may be made to
page 515 of the aforementioned Eurocoat 97 article where the
characteristics of some acrylic polyols are given, these examples
being of a non-limiting nature.
[0167] Hyperbranched polyols which are generally characterised by a
greater functionality than linear polyols may also be used, but
these products are not preferred due to the high viscosity
thereof.
[0168] Structured or block polyols may also be used if it is
desired to compartmentalise the properties. However, these
products, which are generally more expensive, are only used to
produce a specific property. These compounds, are, for example, a
rheological agent or an agent which assists in the dispersion of
pigments.
[0169] Generally, for the requirements of the present invention,
the ratio of isocyanate functions/mobile hydrogen functions is
between 1.5 and 0.5, preferably between 1.2 and 0.8. In particular,
when the mobile hydrogen compound is a polyol, the isocyanate
functions/hydroxyl functions ratio is between 1.5 and 0.5,
preferably between 1.2 and 0.8.
[0170] The present invention also relates to a process for
preparing a hydrophilic polyisocyanate composition as defined
above, comprising a step of mixing the compounds of formulae (I)
and (II), the amine and the (poly)isocyanate.
[0171] When the amine is primary or secondary, it is preferable to
avoid it being present alone with the isocyanate since it can react
and produce urea.
[0172] When using a secondary or primary amine, it is preferable to
proceed to the neutralisation step before adding it to the
polyisocyanate in order to avoid undesired reactions between NCO
groups and the amine. If a tertiary amine is used, it is optionally
possible to mix the amine with the polyisocyanate and then carry
out the neutralisation step by adding the acid part.
[0173] The present invention also relates to a process for
preparing a composition as defined above, in which the amine of the
surfactant is a primary or secondary amine, said process being
characterised in that it comprises a step of mixing the compounds
of formulae (I) and (II) and the amine followed by a step in which
the (poly)isocyanate is added.
[0174] The present invention also relates to a process for
preparing a composition as defined above, in which the amine of the
surfactant is a tertiary amine, said process being characterised in
that it comprises a step of mixing the compounds of formulae (I)
and (II) and the amine, followed by a step in which the
(poly)isocyanate is added, or in that it comprises a step of mixing
the amine and the (poly)isocyanate, followed by a step in which the
compounds of formulae (I) and (II) are added.
[0175] The preparation process of the present invention is carried
at a temperature preferably 5 100.degree. C., advantageously at a
temperature from 15 to 60.degree. C., and even more preferably from
20 to 50.degree. C., preferably working in an inert atmosphere and
avoiding the introduction of water. This is generally preferable to
work at ambient temperature but for specific reasons relating to
viscous polyisocyanate formulations, it is possible to work at
temperatures greater than ambient temperature.
[0176] The present invention also relates to a process for
producing a coated substrate, characterised in that it comprises a
step of applying to a substrate a composition which is
cross-linkable by thermal treatment as defined above, and a step of
cross-linking by thermal treatment of said composition.
[0177] According to an advantageous embodiment, the process as
defined above is characterised in that the cross-linking by thermal
treatment is carried out at a temperature from 60.degree. C. to
300.degree. C., preferably greater than 80.degree. C. and lower
than 300.degree. C., advantageously from 100.degree. C. to
200.degree. C., for a period of time lasting from a few seconds to
a few hours.
[0178] The aforementioned cross-linkable composition may be used as
a first coat (preparation of a coating for original equipment) or
as a secondary coat, in particular as a hardener of the first layer
of a coating or for retouching.
[0179] The present invention also relates to a coated substrate
obtainable from the process as defined above.
[0180] The substrate may be of any type and is generally a metal
substrate, for example aluminium or steel, in particular stainless
steel. The substrate may also be a substrate made of plastics
material, i.e. a thermoplastic or thermosetting polymer material,
optionally comprising fillers, for example reinforcement fillers
such as fibreglass, carbon fibre and the like.
[0181] Due to the properties conferred by the aforementioned
coating, the coated substrate may optionally be folded, moulded or
pressed. The substrate thus coated has excellent resistance to
chipping as well as an excellent resistance to pressure washes,
even high-pressure washes, in particular in the case of plastics
materials substrates.
[0182] Other additive compounds may be added to the coating
formulations, in particular to facilitate implementation or to
protect or embellish. In this context, anti-foaming agents,
pigments or colouring agents or additives conferring resistance to
scratches or graffiti may be mentioned. This type of addition is
well-known to the person skilled in the art or to the formulator of
the coating who will adjust the amounts to the properties required
for the application.
[0183] The fields of application of the new compounds are
adhesives, paints and varnishes, glues, products for treating
textiles or mineral, organic or organic mineral fibres, concrete or
walls. The supports to be coated in this case are wood, metals,
textiles, various celluloses, mineral compounds and glasses.
[0184] Measuring the Acid Value
[0185] The method for measuring the acid value consists of
neutralising the product after it has been dissolved in a suitable
solvent [water or water plus 2.5% Igepal NP-10 (or nonylphenol 10
OE) or water/ethanol at a ratio of 50/501 using a solution of
potassium or sodium hydroxide. pH-metric or potentiometric
titration is used.
[0186] The procedure of this assay method is as follows:
[0187] 1) Preparation of 2 100 mL Solutions:
[0188] Approximately 2 g of the product to be tested are weighed in
a 250 ml beaker and are made up to approximately 100 ml with a
solution of deionised water and, if necessary, for better
dissolution, 2.5% Igepal NP-10 is added. Lastly, the mixture is
stirred until total dissolution is achieved (magnetic
stirring).
[0189] 2) First Assay: Assaying the Two First Acidities
[0190] One of the phosphate ester solutions (prepared in the
preceding step) is titrated with 0.5 N sodium hydroxide with
vigorous stirring (magnetic stirring). Two inflections
corresponding to the first acidity of H.sub.3PO.sub.4, of the
diester and the monoester and secondly to the second acidity of
H.sub.3PO.sub.4 and the second acidity of the monoester
respectively are obtained.
[0191] The volume of the titrant required in order to obtain each
jump is noted: [0192] V.sub.1 for the first equivalence. [0193]
V.sub.2 for the second equivalence.
[0194] 3) Second Assay: Assaying of the Third Acidity
[0195] The second phosphate ester solution is titrated in the same
manner as the previous solution but, just before the second
inflection, 10 ml of a 10% CaCl.sub.2 solution is quickly added
using a syringe which causes a decrease in pH:
2Na.sub.2HPO.sub.4+CaCl.sub.2(PO.sub.4Na.sub.2).sub.2Ca+2HCl
[0196] followed by the third inflection corresponding to the third
acidity of H.sub.3PO.sub.4. The volume, V.sub.3, of titrant
required to obtain the third jump is noted.
[0197] The acid values are thus calculated as follows:
[0198] First Acid Value:
I A 1 = V 1 .times. N .times. 56 , 1 m 1 ##EQU00003##
[0199] Second Acid Value:
I A 2 = V 2 .times. N .times. 56 , 1 m 1 ##EQU00004##
[0200] Third Acid Value:
I A 3 = V 3 .times. N .times. 56 , 1 m 2 ##EQU00005##
[0201] in which V.sub.i=volume of sodium hydroxide solution in ml
[0202] N=normality of the titrant [0203] m.sub.i=weight in g of
phosphate ester titrated in solution i [0204] Molar mass of
KOH=56.1 g
[0205] The molar percentages of H.sub.3PO.sub.4, of monoester and
diester in the ionic phase are calculated as follows:
% H 3 PO 4 = V 3 - V 2 V 1 .times. 100 = I A 3 - I A 2 I A 1
.times. 100 ##EQU00006## % monoester = ( 2 V 2 - V 1 - V 3 ) V 1
.times. 100 = ( 2 I A 2 - I A 1 - I A 3 ) I A 1 .times. 100
##EQU00006.2## % diester = ( 2 V 1 - V 2 ) V 1 .times. 100 = ( 2 I
A 1 - I A 2 ) I A 1 .times. 100 ##EQU00006.3##
[0206] The percentage by weight of H.sub.3PO.sub.4, free monoester
and free diester are calculated as described below.
[0207] In order to calculate the average molar mass, the mole
fractions are used: n(H.sub.3PO.sub.4), n(monoester), n(diester)
and n(ionic), in which:
n(H.sub.3PO.sub.4)=% H.sub.3PO.sub.4/100
[0208] n(monoester)=% monoester/100
[0209] n(diester)=% diester/100
[0210] n(ionic)=% ionic/100
[0211] The average molar mass (MM.sub.av) is thus calculated as
follows:
MM.sub.av=(M(H.sub.3PO.sub.4).times.n(H.sub.3PO.sub.4))+(M(monoester).ti-
mes.n(monoester))+(M(diester).times.n(diester))
[0212] The percent by weight are thus as follows:
% ionic = V 1 .times. N .times. MM av 10 .times. m 1 ##EQU00007## %
H 3 PO 4 = M ( H 3 PO 4 ) MM av .times. n ( H 3 PO 4 ) .times. n (
ionic ) .times. 100 ##EQU00007.2## % monoester = M ( monoester ) MM
av .times. n ( monoester ) .times. n ( ionic ) .times. 100
##EQU00007.3## % diester = M ( diester ) MM av .times. n ( diester
) .times. n ( ionic ) .times. 100 ##EQU00007.4##
EXAMPLES
[0213] The following products were used: [0214] bis(2-ethylhexyl)
phosphate (B2EHP), CAS no. [298-07-7], 97% Aldrich diester
[0214] ##STR00007## [0215] compound of formula (I) in which
R.sub.1.dbd.R.sub.2=2-ethylhexyl dibutylphosphate (PHD) CAS no.
[107-66-4] 97% diester, Aldrich
[0215] ##STR00008## [0216] compound of formula (I) in which
R.sub.1.dbd.R.sub.2=butyl [0217] HORDAPHOS MOB, CAS no.
[12788-93-1], CLAIRANT phosphoric acid ester, mono/diester molar
ratio=7.4 [0218] HORDAPHOS MDB, CAS no. [12788-93-1], CLAIRANT
phosphoric acid ester, mono/diester molar ratio=1.6 [0219] Rhodafac
SS 610 CAS no. [9046-01-9] RHODIA phosphoric acid ethoxyl ester,
mono/diester molar ratio=5.8
TABLE-US-00001 [0219] mg KOH/g Hordaphos MOB Hordaphos MDB Rhodafac
SS 610 First acidity 360 312 103
[0220] DMCHA: N,N-dimethylcyclohexylamine, CAS no. [98-94-2],
BASF
[0220] ##STR00009## [0221] NEM; N-ethylmorpholine, CAS no.
[100-74-3] BASF
[0221] ##STR00010## [0222] EDIPA ethyldiisopropylamine CAS no.
[7087-68-5] BASF
[0222] ##STR00011## [0223] Tolonate HDT (Rhodia): Hexamethylene
diisocyanate (HDI)-based polyisocyanate which is characterised
substantially by the presence of isocyanurate cyclic structures and
characterised to a lesser extent by biuret functions and dimer
cyclic structures (diazetidine dione); its isocyanate function
content is approximately 22%.+-.0.5% by weight and its viscosity is
between 2,000 and 2,800 mPas at 25.degree. C. [0224] Tolonate HDT
LV2 (Rhodia): Hexamethylene diisocyanate (HDI)-based polyisocyanate
which is characterised substantially by the presence of
isocyanurate cyclic structures and characterised to a lesser extent
by biuret functions and dimer cyclic structures (diazetidine
dione); its isocyanate function content is approximately 23%.+-.1%
by weight and its viscosity is between 450 et 750 mPas at
25.degree. C. [0225] SETALUX 6511 AQ-47 (Nuplex): acrylic polyol,
OH %=4.2%, ES=47%, [0226] SETALUX 6520 AQ-45 (Nuplex): acrylic
polyol, OH %=3.2%, ES=45%, [0227] Macrynal 6299 WA 42 (Cytec)
acrylic polyol (Cytec), OH %=4.1%, ES=42%
[0228] Preparation of Surfactants and Hydrophilic Polyisocyanates
for Use with Polyurethane Dispersions
[0229] Phosphate esters were neutralised with amines by means of
simple mixing for 1 hour in a roller pot. The surfactants prepared
previously were mixed in a roller pot for one night with tolonate
HDT or tolonate HDT LV2 in order to prepare the hydrophilic
polyisocyanates.
[0230] The table below summarises the compositions of the various
hydrophilic polyisocyanates (the term `phosphate 1` refers to
unethoxylated phosphate esters):
TABLE-US-00002 Composition by weight (%) Phosphate 1 HDT SS type
HDT LV2 DMCHA NEM EDIPA Phosphate 1 610 Example 1 MOB 88 / 5.60 / /
6.4 / Example 2 B2EHP 88 / 3.4 / / 8.6 / Example 3 MDB 88 / 6.2 / /
5.8 / Example 4 DBP 88 / 4.6 / / 7.4 / Example 5 DBP 93 / 2.05 / /
2.15 2.8 Example 6 DBP 93 / 1.65 / / 0.9 4.45 Example 7 DBP 90 /
2.95 / / 3.05 4 Example 8 DBP 90 / 2.4 / / 1.2 6.4 Example 9 DBP 93
/ 2.45 / / 3.45 1.1 Example 10 DBP 90 / 3.5 / / 4.9 1.6 Example 11
MDB 92 / 3.5 / / 4.5 / Example 12 MDB 92 / / 3.3 / 4.7 / Example 13
MDB 92 / / / 3.5 4.5 / Example 14 MDB / 92 2.6 / / 2.4 3.2 Example
15 MDB / 92 / 2.5 / 2.3 3.2 Example 16 MDB / 92 / / 2.6 2.3 3.1
Example 17 MDB 92 / 2.6 / / 2.4 3.2 Example 18 MDB 92 / / 2.5 / 2.3
3.2 Example 19 MDB 92 / / / 2.6 2.3 3.1
[0231] Application Results
[0232] 1) Evaluation of Dispersibility in Water
[0233] Particle size was measured using a Mastersizer 2000
laser-type granulometer from Malvern. The average particle size
corresponding to 50% and 90% of the population by volume is
given.
TABLE-US-00003 Product example Monoester/diester No. molar ratio
d.sub.50 (.mu.m) d.sub.90 (.mu.m) 5 0.4 15.5 23.9 6 1.2 0.1 0.4 7
0.4 9.8 16.8 8 1.2 0.1 0.1 9 0.1 58.3 92.8 10 0.1 24.7 39.3 18 2.1
0.097 0.097 19 2.1 0.114 0.114
[0234] The products with monoester/diester ratios lower than 1 have
particle sizes greater than a micron and are not easily
self-emulsifiable.
[0235] 2) Preparation of a Polyurethane Dispersion-Based Formula
for Floor Varnish
[0236] The polyisocyanates of examples 1 to 4 were diluted with 30%
butyl glycol acetate in order to be ready for use. A formulation
consisting of 10 parts of a commercial part A from BONA (ref Flow)
and of 1 part polyisocyanates diluted in the butyl glycol acetate
was then produced. The mixture was hand-made in a 50 ml beaker.
After 10 mins of rest the compositions were applied to Leneta
plates and left at a regulated temperature and humidity (23.degree.
C., 50% RH) for 7 days. Shine at 60.degree. was then measured using
a glossmeter (BYK) and the visual appearance of the film was
assessed using a scale of 1 to 10. [0237] 1: film having no defects
[0238] 10: completely heterogeneous film having traces of gels or
dewetting.
[0239] The following table shows the results obtained:
TABLE-US-00004 Quality of the Product of the Example mixture Film
score example Example 20 RAS 2 1 Example 21 heterogeneous 10 2
Example 22 RAS 3 3 Example 23 curd 8 4
[0240] Examples 21 and 23, prepared based on pure diesters, have a
very poor visual appearance.
[0241] For the examples prepared from mixtures of mono and
diesters, it is possible to obtain films which have a satisfactory
visual appearance (examples 20 and 22).
[0242] The hydrophilic polyisocyanate of Example 1 was again used
in the same conditions but a different solvent was used to dilute
the polyisocyanate.
[0243] The table below shows the results with regard to shine and
film appearance.
TABLE-US-00005 Example Mixture 60.degree. Film score Solvent
Example 24 RAS 84 2 butyl glycol acetate Example 25 RAS 87 3
ProGlyde DMM (Dow) Example 26 RAS 85 3 Rhodiasolv RPDE (Rhodia)
[0244] The results are comparable for the three solvents and
indicate that the formulation is robust to changes in the nature of
the solvents.
[0245] 3) Preparation of an Acrylic Polyol-Based Formula for Metal
Application:
[0246] The polyol used was an acrylic-type polyol (Macrynal 6299
from Cytec) titrant 4.1% OH. Part A was prepared by mixing the
following ingredients in order:
TABLE-US-00006 Amount (g) Function Supplier Macrynal VSM 6299W/42WA
83.75 polyol Cytec Borchi gel LW44 (50% in 0.5 thickener Borchers
H2O) Butoxyl 4.8 solvent Celanese Proglyde DMM 0.95 solvent Dow
BYK346 0.95 wetting agent Byk Borch GOL LAC 80 (10% 1.45 levelling
Borcher in butoxyl) agent H.sub.2O 7.6
[0247] The end formulation was produced by mixing part A with the
polyisocyanates of Examples 1 and 3 in accordance with the
following conditions:
TABLE-US-00007 Example 27 Example 28 Part A (g) 80.02 80.22
Polyisocyanate of Example 1 30.84 / Polyisocyanate of Example 3 /
30.62 Butoxyl (g) 7.75 7.74 Water added (g) 31.13 30.71 Viscosity
cup DIN 4 25''17 23''59
[0248] The formulations were then applied using a film applicator
to a glass plate and shine was measured after 7 days of storage in
a controlled atmosphere (23.degree. C. et 50% relative
humidity).
TABLE-US-00008 Test Example 27 Example 28 Thickness 61 .mu.m 64
.mu.m Shine at 20.degree. 89 84 Haze 26 65
[0249] The use of the products which are the subject of the
invention in this formula makes it possible to obtain coatings
which are of high visual quality with low haze values. This
indicates improved compatibility.
[0250] 4) Preparation of an Acrylic Varnish Formula for Plastics
Material Application
[0251] Firstly, a mixture of additives was prepared in accordance
with the following composition: (Dispermat at 2000 rpm)
TABLE-US-00009 Product % by weight Function Producer Butyl glycol
44 Co-solvent Dehydran 1293 20.6 Anti-foaming agent Cognis BYK 301
13.1 Slip agent BYK Chemie BYK 348 22.3 Wetting agent BYK
Chemie
[0252] Preparation of part A on Dispermat at 2000 rpm
[0253] Each ingredient according to the following composition was
added progressively. Next, all of the ingredients were stirred at
3000 rpm for 20 min.
TABLE-US-00010 Product Weight (g) Nature Producer Setalux 6511 AQ47
509 Acrylic polyol Nuplex Setalux 6520 AQ45 176 Acrylic polyol
Nuplex H.sub.2O (demineralised) 80 DMEA (dimethyl 3.8
Neutralisation agent ethanol amine) Additive mixture 24.2 BGA
(butyl glycol 70 Co-solvent acetate) H.sub.2O (demineralised)
137
[0254] The amount of polyisocyanate necessary to achieve a NCO/OH
ratio of 1.4 and, optionally, a solvent for diluting the
polyisocyanate were added in a 250 ml beaker to "part A".
TABLE-US-00011 Product of Example the Part A Part B Butoxyl ref.
example (g) (g) (g) 29 5 100 21.3 / 30 6 100 21.3 / 31 7 100 21.8 /
32 8 100 21.8 / 33 9 100 21.3 / 34 10 100 21.8 / 35 11 100 21.4 5.4
36 12 100 21.4 5.4 37 13 100 21.4 5.4 38 14 100 20.4 5.1 39 15 100
20.4 5.1 40 16 100 20.4 5.1 41 17 100 21.4 / 42 18 100 21.4 / 43 19
100 21.4 /
[0255] 12 g demineralised water were added after application in
order to reduce viscosity.
[0256] All of the ingredients were mixed for 60 seconds using a
viscometer (model 33271 ERICHSEN).
[0257] After 10 min of rest, the mixture was applied using an
ERICHSEN automatic film applicator (model 509/3) at a speed of 18
mm/s to two glass plates for a wet thickness of 200 .mu.m.
[0258] The plates were desolventised for 15 min at ambient
temperature then cured in a furnace for 30 min at 80.degree. C.
[0259] After curing, the plates were kept in a conditioned
atmosphere (23.degree. C., 50% humidity). Shine at 20.degree. was
then measured using a glossmeter (BYK). The shine and haze values
(indicating the visual quality of the film) are shown in the
following table:
TABLE-US-00012 Product example Monoester/diester Example ref. no.
Molar ratio gloss 20.degree. haze 27 5 0.4 67 305 28 6 1.2 94 29 29
7 0.4 65 346 30 8 1.2 93 57 31 9 0.1 56 352 32 10 0.1 64 324 33 11
1.6 92 90 34 12 1.6 89 126 35 13 1.6 96 57 36 14 2.1 96 38 37 15
2.1 98 20 38 16 2.1 97 27 39 17 2.1 96 22 40 18 2.1 93 48 41 19 2.1
99 22
[0260] The compositions having a monoester/diester ratio lower than
1 are characterised by lower shine values and higher haze
values.
* * * * *